Process of manufacturing rubberlike products



Patented June 5, 1928 UNITED. STATES PATENT OFFICE.

WIIaLY O. HEBRMANN AND WOLFRAM HAEHNEL, OI MUNICH GERMANY, ASSIGNOBS TO GDNSORTIUMIUEB ELEKTROCHEMISCHE INDUSTRIE, OF MUNICH, GERMANY.

- riaocass or manurac'runmo RUBBERLIKE raonuc'rs.

No Drawing. Application filed November 8, 1920, Serial no. 147,180, and in Germany November 28, 1025.

We have found a process of manufacturing rubber like products from polymerized vinyl compounds. These polymerized vinyl compounds are polymerized vinyl alcohol or derivatives thereof such as esters, ethers, acetals and the like. Vinyl alcohol itself is a theoretical material. of which we have discovered a polymerized form as described in our copending ap lication, S. N. 44,410 filed July 17, 1925. his cohol can be obtained by acid or alkaline saponification of vinyl esters or polymerized vinyl esters.

As an example of preparation of such a polymerized vinyl alcohol the following is iven: 60 grams of potassium hydroxidev are issolved in 50 grams of ethyl alcohol in a vessel equippedwith a stirrer. Tothis solution are added with thorough agitation, 60 grams of ground polymerized vinyl acetate. After agitating about half an hour the precipitated Ipolymer of vinyl alcohol is separated on a ter and dried.

This polymer of vinyl'alcohol is a water soluble powder having no odor, of white color and a formula of (CI-I =CHOH)n wherein n is varying but-has an average value of 18 to 20. This polymer undergoes the reaction theoretically expected of the alcohol and derivatives of vinyl alcohol can be prepared therefrom. For example; if polymerized vinyl alcohol is treated with butyric anhydride 9. vinyl butyrate is formed; vinyl P aleuritinate trioxystearate or glycollate can be prepared-from the vinyl alcohol polymer and the correspondin acids; if a solution of polymerized vinyl a cohol and sodium hyroxide is evaporated the sodium alcoholate is formed. I

The process of this invention consists in treating polymerized vinyl alcohol or its derivatives with sulphur or sulphur compounds under application of heat. This treatment, causes a combination of the yl compounds with. the sulphur and is similar to that of vulcanizing rubber and therefor the process is referred to as a vulcanization process in the specification'and claims. Similarly also, accelerators or catalysts for this reaction may be em loyed.

ccording to the conditions under which the reaction is carried out for instance the duration of heating or pressing, the temperature used, the pressure chosen and accordolymerized vinyl al-'- ing to the pro erties of the starting material a variety of ifierent products may be ob-' tamed more or less similar to different qualit es of soft or hard rubber but beside. this zvith specific chemical and technical properies.

The following examples show some modes of executing our process and some products obtainable by our process but we w1sh to be understood that our process is not limited to these examples but comprises also other methods for executing this new reaction of sulfur and its compounds on polymeric vinyl alcohol and their derivatives as stated above,

also other products of this vulcanizing process.

Ewample I Pol meric vinyl alcohol which was obtalne accordin to our ap lication S. N. 44,410 was mixed with 1% sn fur and treated for 5 hours at 150 C. under a pressure of 10 atmospheres. The reaction roduct obtamed was a black hard rubberli e material which can be worked by cutting, sawing, filmg or the like.

Ewample I l Polymeric vinyl alcohol was mixed with 2% sulfur and. 2% Eiperidine as accelerator. This mixture was eated only for half an hour at 120 C. under-pressure of 10 atmosheres.

The black hard rubberlike material as in Example I.

Eayomple 1.11. Polymeric vinyl alcohol which was obtained according to our application S. N. 44,410 was covered at ordinar temperature product obtained was about the same with a 10 per cent solution 0 sulfur monochloride in carbondisulfide. After 24 hours the liquid was removed and the reaction product washed with hot water. This reaction product obtained was a grey coloured plastic material similar to vulcanized soft rubber.

Ewample IV.

I 1000 ams of a .30 per cent solution of polymerized vinyl acetate in 96 per cent was a hard and elastic material of yellowish grey colour.

The new products obtained according to this vulcanizing process can be directly used for a variety of technical purposes and in the arts. They can be worked intodesired shapes in various ways by pressing, cutting, sawing, filing and the like for themselves or in mixture with additional materials such as fillers and the like.

But it is also possible to mix other additional substances like coloring matters, fillers for instance cotton flocks or other fibrous material, ground cork or other material used in the manufacture of moulded articles to ,the starting material and to subject this mixture to the vulcanizing process as described. The Vvulcanizing process under pressure can be carried out in suitable presses and the vulcanized material thus directly obtained in the desired form.

Ewwmple V.

like products by treating polymeric vinyl compounds with sulfur compounds.

4. The process of manufacturing rubber like products by treating polymeric vinyl compounds with sulfur and accelerators.

5. The process of manufacturing rubber like products by treating polymeric vinyl compounds with sulfur compounds and accelerators.

6. The process of manufacturing rubber like products by subjecting polymeric vinyl compounds to a vulcanizing process under pressure.

7. The process of manufacturing rubber like products by subjecting polymeric vinyl compounds to a vulcanizing process under heating.

8. The process of manufacturing rubber like products by subjecting polymeric vinyl compounds to a vulcanizing process under pressure and heating.

9. The process of manufacturing rubber like products by subjecting polymeric vinyl compounds in mixture with additional substances to a vulcanizing process.

10. The process of manufacturing rubber like products by subjecting polymeric vinyl compounds in mixture with additional substances to a vulcanizing process under pressure.

11. The process of'manufacturing rubber ,like products by subjecting polymeric vinyl compounds in mixture with additional substances to a vulcanizing process under heat- 1n T2. The process of manufacturing rubber like products by subjecting polymeric vinyl compounds in mixture with additional substances to a vulcanizing process under pressure and heating.

13. As a product of manufacture vulcanized polymeric vinyl compounds obtained by subjecting polymeric Vinyl compounds to a Vulcanizing process.

14. As a product of manufacture vulcanized polymeric vinyl compounds in mixture with additional substances.

15. As a new product vulcanized vinyl compounds.

WILLY O. HERRMANN. WOLFRAM HAEHNEL.

polymeric 

